Process for separating a fluoroolefin from HF by liquid-liquid extraction

ABSTRACT

Disclosed is a process for separating fluoroolefin from a composition comprising HF and fluoroolefin, said process comprising extracting said composition with an extractant. Also disclosed is a composition comprising HF, at least one fluoroolefin, and at least one extractant.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application claims the priority benefit of U.S. ProvisionalApplication No. 60/830,938, filed Jul. 13, 2006.

BACKGROUND OF THE INVENTION

1. Field of the Disclosure

This disclosure relates in general to a process for the separation ofhydrogen fluoride from fluoroolefins by extraction. In particular, theprocess for separation of hydrogen fluoride from fluoroolefins comprisesliquid-liquid extraction

2. Description of the Related Art

The chemical manufacture of fluoroolefins often produces mixtures of thedesired fluoroolefins and hydrogen fluoride (HF). The separation offluoroolefins from these mixtures is not always easily accomplishedbecause many fluoroolefins form an azeotrope with HF. Existing methodsof distillation and decantation are very often ineffective for theseparation of these compounds. Aqueous scrubbing may be effective, butrequires the use of large amounts of scrubbing solutions and producesexcessive waste and a wet product that must then be dried.

WO 98/00379 discloses the use of sulfuric acid as extractant to separateHF from a fluorocarbon (e.g. HFC-245fa or HFC-356mcfq) by preferentiallyextracting the HF into the sulfuric acid phase. WO 98/00380 discloses asimilar extraction process utilizing water to preferentially extract theHF. US 2001/0004961 A1 discloses the use of hydrocarbon and halocarbonsolvents to remove HF from mixtures with hydrofluoroalkanes of formulaC_(a)H_((2a+2)−b)F_(b), wherein a=3 to 6 and b=1 to 2a+1, byliquid-liquid extraction.

Some fluoroolefins have been found to form azeotropes with hydrogenfluoride, complicating their separation. Aqueous and caustic scrubbingcan be effective, but the valuable HF is converted to a waste andadditional equipment is needed to dry the wet fluoroolefin produced.Therefore, there is a need for new methods of separating fluoroolefinsfrom HF.

SUMMARY OF THE INVENTION

The present disclosure relates to a process for separating afluoroolefin from a composition comprising HF and fluoroolefin, saidprocess comprising extracting said composition with an extractant.

The present disclosure further relates to a composition comprising HF,at least one fluoroolefin, and at least one extractant.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are illustrated in the accompanying figures to improveunderstanding of concepts as presented herein.

FIG. 1 includes an illustration of a process to separate fluoroolefinfrom a composition comprising HF and fluoroolefin by liquid-liquidextraction wherein the extractant has a lower density than thecomposition comprising HF and fluoroolefin.

FIG. 2 includes an illustration of a process to separate fluoroolefinfrom a composition comprising HF and fluoroolefin by liquid-liquidextraction wherein the extractant has a higher density than thecomposition comprising HF and fluoroolefin.

Skilled artisans appreciate that objects in the figures are illustratedfor simplicity and clarity and have not necessarily been drawn to scale.For example, the dimensions of some of the objects in the figures may beexaggerated relative to other objects to help to improve understandingof embodiments.

DETAILED DESCRIPTION OF THE INVENTION

The present disclosure relates to a process for separating afluoroolefin from a composition comprising HF and fluoroolefin, saidprocess comprising extracting said composition with an extractant.

In one embodiment, the process for separating a fluoroolefin from acomposition comprising HF and fluoroolefin by extracting saidcomposition with an extractant, wherein said extracting comprises aliquid-liquid extraction.

In one embodiment, the process for separating fluoroolefin from acomposition comprising HF and fluoroolefin by extracting saidcomposition with an extractant, may use extractants selected from thegroup consisting of hydrocarbons, chlorocarbons, chlorofluorocarbons,hydrochlorofluorocarbons, hydrofluorocarbons, perfluorocarbons, andperfluorinated ethers.

In one embodiment the process for separating fluoroolefin from acomposition comprising HF and fluoroolefin, comprises:

-   -   a. feeding a composition comprising HF and fluoroolefin and a        composition comprising extractant to an extractor; and    -   b. removing from said extractor an extractant-rich phase        comprising extractant and fluoroolefin.

Optionally, in another embodiment the process for separatingfluoroolefin from a composition comprising HF and fluoroolefin furthercomprises:

-   -   a. feeding the extractant-rich phase comprising extractant and        fluoroolefin to an extractant recovery column; and    -   b. recovering fluoroolefin product essentially free of        extractant from the extractant recovery column.

In another embodiment the process separating fluoroolefin from acomposition comprising HF and fluoroolefin comprises:

-   -   a. feeding a composition comprising HF and fluoroolefin and a        composition comprising extractant to an extractor; and    -   b. removing from said extractor an HF-rich phase.

Optionally, in another embodiment the process for separatingfluoroolefin from a composition comprising HF and fluoroolefin furthercomprises:

-   -   a. feeding said HF-rich phase to a raffinate stripping column;        and    -   b. recovering from said raffinate stripping column an HF product        essentially free of fluoroolefin and extractant.

In yet another embodiment the process for separating fluoroolefin from acomposition comprising HF and fluoroolefin comprises:

-   -   a. feeding a composition comprising HF and fluoroolefin and a        composition comprising extractant to an extractor;    -   b. removing from said extractor an extractant-rich phase        comprising extractant and fluoroolefin;    -   c. removing from said extractor an HF-rich phase;    -   d. feeding said extractant-rich phase comprising extractant and        fluoroolefin to an extractant recovery column;    -   e. recovering fluoroolefin product essentially free of        extractant from the extractant recovery column;    -   f. feeding said HF-rich phase to a raffinate stripping column    -   g. recovering from said raffinate stripping column HF product        essentially free of fluoroolefin and extractant.

In one embodiment, said extractor operates at a pressure of from about14.7 psia to about 300 psia and a temperature from about −50° C. toabout 150° C.

In one embodiment, said extractant recovery column operates at apressure of about 14.7 psia to about 300 psia and a top temperature ofabout −50° C. to about 100° C. and a bottom temperature of about 50° C.to about 250° C.

In one embodiment, said raffinate stripping column operates at apressure of about 14.7 psia to about 100 psia and a top temperature ofabout −50° C. to about 90° C. and a bottom temperature from about 20° C.to about 150° C.

The present disclosure further provides a composition comprising:

-   -   a. HF,    -   b. at least one fluoroolefin, and    -   c. at least one extractant.

In one embodiment, the extractant may be at/least one compound selectedfrom the group consisting of hydrocarbons, chlorocarbons,chlorofluorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons,perfluorocarbons, and perfluorinated ethers.

In some embodiments, said fluoroolefin is selected from the groupconsisting of:

-   -   (i) fluoroolefins of the formula E- or Z—R¹CH═CHR², wherein R¹        and R² are, independently, C₁ to C₆ perfluoroalkyl groups;    -   (ii) cyclic fluoroolefins of the formula        cyclo-[CX═CY(CZW)_(n)—], wherein X, Y, Z, and W, independently,        are H or F, and n is an integer from 2 to 5; and    -   (iii) fluoroolefins selected from the group consisting of:        tetrafluoroethylene (CF₂═CF₂); hexafluoropropene (CF₃CF═CF₂);        1,2,3,3,3-pentafluoro-1-propene (CHF═CFCF₃),        1,1,3,3,3-pentafluoro-1-propene (CF₂═CHCF₃),        1,1,2,3,3-pentafluoro-1-propene (CF₂═CFCHF₂),        1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF₂),        2,3,3,3-tetrafluoro-1-propene (CH₂═CFCF₃),        1,3,3,3-tetrafluoro-1-propeneCHF═CHCF₃),        1,1,2,3-tetrafluoro-1-propene (CF₂═CFCH₂F),        1,1,3,3-tetrafluoro-1-propene (CF₂═CHCHF₂),        1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF₂),        3,3,3-trifluoro-1-propene (CH₂═CHCF₃), 2,3,3-trifluoro-1-propene        (CHF₂CF═CH₂); 1,1,2-trifluoro-1-propene (CH₃CF═CF₂);        1,2,3-trifluoro-1-propene (CH₂FCF═CF₂);        1,1,3-trifluoro-1-propene (CH₂FCH═CF₂);        1,3,3-trifluoro-1-propene (CHF₂CH═CHF);        1,1,1,2,3,4,4,4-octafluoro-2-butene (CF₃CF═CFCF₃);        1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₃CF₂CF═CF₂);        1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF═CHCF₃);        1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF₂CF₃);        1,1,1,2,3,4,4-heptafluoro-2-butene (CHF₂CF═CFCF₃);        1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene ((CF₃)₂C═CHF);        1,1,3,3,4,4,4-heptafluoro-1-butene (CF₂═CHCF₂CF₃);        1,1,2,3,4,4,4-heptafluoro-1-butene (CF₂═CFCHFCF₃);        1,1,2,3,3,4,4-heptafluoro-1-butene (CF₂═CFCF₂CHF₂);        2,3,3,4,4,4-hexafluoro-1-butene (CF₃CF₂CF═CH₂);        1,3,3,4,4,4-hexafluoro-1-butene (CHF═CHCF₂CF₃);        1,2,3,4,4,4-hexafluoro-1-butene (CHF═CFCHFCF₃);        1,2,3,3,4,4-hexafluoro-1-butene (CHF═CFCF₂CHF₂);        1,1,2,3,4,4-hexafluoro-2-butene (CHF₂CF═CFCHF₂);        1,1,1,2,3,4-hexafluoro-2-butene (CH₂FCF═CFCF₃);        1,1,1,2,4,4-hexafluoro-2-butene (CHF₂CH═CFCF₃);        1,1,1,3,4,4-hexafluoro-2-butene (CF₃CH═CFCHF₂);        1,1,2,3,3,4-hexafluoro-1-butene (CF₂═CFCF₂CH₂F);        1,1,2,3,4,4-hexafluoro-1-butene (CF₂═CFCHFCHF₂);        3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH₂═C(CF₃)₂);        1,1,1,2,4-pentafluoro-2-butene (CH₂FCH═CFCF₃);        1,1,1,3,4-pentafluoro-2-butene (CF₃CH═CFCH₂F);        3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂);        1,1,1,4,4-pentafluoro-2-butene (CHF₂CH═CHCF₃);        1,1,1,2,3-pentafluoro-2-butene (CH₃CF═CFCF₃);        2,3,3,4,4-pentafluoro-1-butene (CH₂═CFCF₂CHF₂);        1,1,2,4,4-pentafluoro-2-butene (CHF₂CF═CHCHF₂);        1,1,2,3,3-pentafluoro-1-butene (CH₃CF₂CF═CF₂);        1,1,2,3,4-pentafluoro-2-butene (CH₂FCF═CFCHF₂);        1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF₂═C(CF₃)(CH₃));        2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH₂═C(CHF₂)(CF₃));        2,3,4,4,4-pentafluoro-1-butene (CH₂═CFCHFCF₃);        1,2,4,4,4-pentafluoro-1-butene (CHF═CFCH₂CF₃);        1,3,4,4,4-pentafluoro-1-butene (CHF═CHCHFCF₃);        1,3,3,4,4-pentafluoro-1-butene (CHF═CHCF₂CHF₂);        1,2,3,4,4-pentafluoro-1-butene (CHF═CFCHFCHF₂);        3,3,4,4-tetrafluoro-1-butene (CH₂═CHCF₂CHF₂);        1,1-difluoro-2-(difluoromethyl)-1-propene (CF₂═C(CHF₂)(CH₃));        1,3,3,3-tetrafluoro-2-methyl-1-propene (CHF═C(CF₃)(CH₃));        3,3-difluoro-2-(difluoromethyl)-1-propene (CH₂═C(CHF₂)₂);        1,1,1,2-tetrafluoro-2-butene (CF₃CF═CHCH₃);        1,1,1,3-tetrafluoro-2-butene (CH₃CF═CHCF₃);        1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF₃CF═CFCF₂CF₃);        1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF₂═CFCF₂CF₂CF₃);        1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene        ((CF₃)₂C═CHCF₃); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene        (CF₃CF═CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene        (CF₃CH═CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene        (CHF═CFCF₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene        (CF₂═CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene        (CF₂═CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene        (CHF₂CF═CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene        (CF₃CF═CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene        (CF₃CF═CFCHFCF₃);        1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene        (CHF═CFCF(CF₃)₂);        1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene        (CF₂═CFCH(CF₃)₂);        1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene        (CF₃CH═C(CF₃)₂);        1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene        (CF₂═CHCF(CF₃)₂); 2,3,3,4,4,5,5,5-octafluoro-1-pentene        (CH₂═CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene        (CHF═CFCF₂CF₂CHF₂);        3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene        (CH₂═C(CF₃)CF₂CF₃);        1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene        (CF₂═CHCH(CF₃)₂);        1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene        (CHF═CHCF(CF₃)₂);        1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene        (CF₂═C(CF₃)CH₂CF₃);        3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene        ((CF₃)₂CFCH═CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene        (CF₃CF₂CF₂CH═CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene        (CH₂═CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene        (CF₂═CHCF₂CH₂CF₃); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene        (CF₃CF═C(CF₃)(CH₃));        2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene        (CH₂═CFCH(CF₃)₂);        1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene        (CHF═CHCH(CF₃)₂);        1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene        (CH₂FCH═C(CF₃)₂);        1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene        (CH₃CF═C(CF₃)₂); 1,1,1-trifluoro-2-(trifluoromethyl)-2-butene        ((CF₃)₂C═CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene        (CF₃CF₂CF═CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene        (CF₃C(CH₃)═CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene        (CH₂═CHCF₂CHFCF₃); 4,4,4-trifluoro-2-(trifluoromethyl)-1-butene        (CH₂═C(CF₃)CH₂CF₃);        1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF₃(CF₂)₃CF═CF₂);        1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene        (CF₃CF₂CF═CFCF₂CF₃);        1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene        ((CF₃)₂C═C(CF₃)₂);        1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene        ((CF₃)₂CFCF═CFCF₃);        1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene        ((CF₃)₂C═CHC₂F₅);        1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene        ((CF₃)₂CFCF═CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene        (CF₃CF₂CF₂CF₂CH═CH₂);        4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene        (CH₂═CHC(CF₃)₃);        1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene        ((CF₃)₂C═C(CH₃)(CF₃));        2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene        (CH₂═CFCF₂CH(CF₃)₂);        1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene        (CF₃CF═C(CH₃)CF₂CF₃);        1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene        (CF₃CH═CHCH(CF₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene        (CF₃CF₂CF₂CF═CHCH₃); 3,3,4,4,5,5,6,6-octafluoro1-hexene        (CH₂═CHCF₂CF₂CF₂CHF₂);        1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene        ((CF₃)₂C═CHCF₂CH₃);        4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene        (CH₂═C(CF₃)CH₂C₂F₅);        3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene        (CF₃CF₂CF₂C(CH₃)═CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene        (CF₃CF₂CF₂CH═CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene        (CH₂═CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene        (CF₃CF₂CF═CFC₂H₅);        4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene        (CH₂═CHCH₂CF(CF₃)₂);        1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene        (CF₃CF═CHCH(CF₃)(CH₃));        1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene        ((CF₃)₂C═CFC₂H₅);        1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene        (CF₃CF═CFCF₂CF₂C₂F₅);        1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene        (CF₃CF₂CF═CFCF₂C₂F₅);        1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene        (CF₃CH═CFCF₂CF₂C₂F₅);        1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene        (CF₃CF═CHCF₂CF₂C₂F₅);        1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene        (CF₃CF₂CH═CFCF₂C₂F₅); and        1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene        (CF₃CF₂CF═CHCF₂C₂F₅).

In certain embodiments, said extractant is selected from the groupconsisting of:

ethane, ethylene, n-propane, propylene, n-butane, isobutane,cyclobutane, 1-butene, 2-butene (cis or trans), n-pentane, isopentane(2-methylbutane), neopentane (2,2-dimethylpropane), cyclopentane,1-pentene, 2-pentene (cis or trans), cyclopentene, n-hexane,cyclohexane, 2-methylpentane, 3-methylpentane, 1-hexene, 2-hexene (cisor trans), 3-hexene (cis or trans), neohexane (2,2-dimethylbutane),neohexene (3,3-dimethyl-1-butene), 2,2-dimethylbutane,2,3-dimethylbutane, 2,3-dimethyl-2-butene, 2,3-dimethyl-1-butene,3,3-dimethyl-1-butene, n-heptane, 1-heptene, 2-heptene (cis or trans),3-heptene (cis or trans), cycloheptene, octane (all isomers), nonane(all isomers), decane (all isomers), undecane (all isomers), dodecane(all isomers), benzene, toluene, tetrachloroethylene, trichloroethylene,1,1-dichloroethylene, 1,2-dichloroethylene, carbon tetrachloride(tetrachloromethane), chloroform (trichloromethane), methylene chloride(dichloromethane), 1,1,2,2-tetrachloroethane, 1,1,1,2-tetrachloroethane,1,1,2-trichloroethane, 1,1,1-trichloroethane,1,1,1,3,3,3-hexachloropropane, dichlorodifluoromethane (CFC-12),fluorotrichloromethane (CFC-11), fluoropentachloroethane (CFC-111),1,2-difluoro-1,1,2,2-tetrachloroethane (CFC-112),1,1-difluoro-1,2,2,2-tetrachloroethane (CFC-112a),1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113),1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a),1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114),1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a), andchloropentafluoroethane (CFC-115),1,1,1,2,3-pentafluoro-2,3,3-trichloropropane (CFC-215bb),2,2-dichloro-1,1,1,3,3,3-hexafluoropropane (CFC-216aa),2,3-dichloro-1,1,1,2,3,3-hexafluoropropane (CFC-216ba),2-chloro-1,1,1,2,3,3,3-heptafluoropropane (CFC-217ba),dichlorofluoromethane (HCFC-21), 1,1,2-trichloro-2,2-difluoroethane(HCFC-122), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123),1,2-dichloro-1,1,1-trifluoroethane (HCFC-123a),2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124),1-chloro-1,1,2,2-tetrafluoroethane (HCFC-124a),1-chloro-1,2,2-trifluoroethane (HCFC-133),2-chloro-1,1,1-trifluoroethane (HCFC-133a), 1,1-dichloro-2-fluoroethane(HCFC-141a), 1,1-dichloro-1-fluoroethane (HCFC-141b),1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-1,1-difluoroethane(HCFC-142b), 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane(HFC-63-14mcee), 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, HFC-162-13mczy,1,2,3,3,3-pentafluoro-1-propene (HFC-1225ye),1,1,3,3,3-pentafluoro-1-propene (HFC-1225zc),1,3,3,3-tetrafluoro-1-propene (HFC-1234ze),2,3,3,3-tetrafluoro-1-propene (HFC-1234yf), 3,3,3-trifluoro-1-propene(HFC-1243zf), 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429myz),1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429mzy),1,1,1,4,4,4-hexafluoro-2-butene (F11E),1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E),1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluoro-3-octene (F24E),1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluoro-4-octene (F33E),fluorobenzene, octafluoropropane (PFC-218), octafluorocyclobutane(PFC-C318), all isomers of C₄F₁₀ (PFC-31-10), hexafluoropropylene (HFP,PFC-1216), all isomers of C₅F₁₂ (PFC-41-12), all isomers of C₆F₁₄(PFC-51-14), PMVE (perfluoromethylvinylether), PEVE(perfluoroethylvinylether), and mixtures thereof.

In one embodiment, the present composition comprises:

-   -   a. from about 5 weight percent to about 15 weight percent, HF;    -   b. from about 30 weight percent to about 80 weight percent        fluoroolefin; and    -   c. from about 5 weight percent to about 70 weight percent        extractant.

In certain embodiments, in the process of purifying fluoroolefin from acomposition comprising HF and fluoroolefin, the fluoroolefin comprises afluoropropene. In one embodiment, the fluoroolefin is Z-HFC-1225ye,E-HFC-1225ye, or any combination or mixture of both isomers in anyratio. In another embodiment, the fluoroolefin is HFC-1234yf. In anotherembodiment, the fluoroolefin is Z-HFC-1234ze, E-HFC-1234ze, or anycombination or mixture of both isomers in any ratio.

In certain embodiments, in the composition comprising HF, at least onefluoroolefin, and at least one extractant, the at least one fluoroolefincomprises a fluoropropene. In one embodiment, the fluoroolefin isZ-HFC-1225ye, E-HFC-1225ye, or any combination or mixture of bothisomers in any ratio. In another embodiment, the fluoroolefin isHFC-1234yf. In another embodiment, the fluoroolefin is Z-HFC-1234ze,E-HFC-1234ze, or any combination or mixture of both isomers in anyratio.

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description, and from theclaims. The detailed description first addresses Definitions andClarification of Terms followed by the Compositions, SeparationProcesses and finally Examples.

1. Definitions and Clarification of Terms

Before addressing details of embodiments described below, some terms aredefined or clarified.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

As used herein, an extractant is defined as a fluid that preferentiallydissolves or extracts one or more chemical compound from a mixture ofchemical compounds and is partially to completely immiscible with one ormore of the other constituents of the chemical compound mixture. In thisway, it is possible to partially to completely transfer one or morepreferentially dissolved chemical compounds from the original mixture ofchemical compounds to a second phase formed by the extractant. In theliquid-liquid extraction art, the term “solvent” is often used insteadof extractant.

As used herein, when a product on any process step is said to be“essentially free of” any substance is meant that the process stepproduces a compound that contains less than about 100 ppm (weight basis)of the substance. In another embodiment the compound produced containsless than about 10 ppm of the substance. In yet another embodiment thecompound produced contains less than about 1 ppm, of the substance.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

2. Compositions

Hydrogen fluoride (HF, anhydrous) is a commercially available chemicalor can be produced by methods known in the art.

The term “fluoroolefin” is intended to mean a compound comprising carbonand fluorine and optionally hydrogen that additionally comprises atleast one double bond.

In one embodiment, fluoroolefins comprise compounds with 2 to 12 carbonatoms, in another embodiment the fluoroolefins comprise compounds with 3to 10 carbon atoms, and in yet another embodiment the fluoroolefinscomprise compounds with 3 to 7 carbon atoms. Representativefluoroolefins include but are not limited to all compounds as listed inTable 1, Table 2, and Table 3.

The present invention provides fluoroolefins having the formula E- orZ—R¹CH═CHR² (Formula I), wherein R¹ and R² are, independently, C₁ to C₆perfluoroalkyl groups. Examples of R¹ and R² groups include, but are notlimited to, CF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂, CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃,CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃, CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅,CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₂C₂F₅, and C(CF₃)₂CF₂C₂F₅. In oneembodiment the fluoroolefins of Formula I, have at least 4 carbon atomsin the molecule. In yet another embodiment, the fluoroolefins of FormulaI have at least 5 carbon atoms in the molecule. Exemplary, non-limitingFormula I compounds are presented in Table 1.

TABLE 1 Code Structure Chemical Name F11E CF₃CH═CHCF₃1,1,1,4,4,4-hexafluorobut-2-ene F12E CF₃CH═CHC₂F₅1,1,1,4,4,5,5,5-octafluoropent-2-ene F13E CF₃CH═CHCF₂C₂F₅1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene F13iE CF₃CH═CHCF(CF₃)₂1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene F22EC₂F₅CH═CHC₂F₅ 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene F14ECF₃CH═CH(CF₂)₃CF₃ 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene F14iECF₃CH═CHCF₂CF—(CF₃)₂1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene F14sECF₃CH═CHCF(CF₃)—C₂F₅1,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)hex-2-ene F14tECF₃CH═CHC(CF₃)₃1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene F23EC₂F₅CH═CHCF₂C₂F₅ 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene F23iEC₂F₅CH═CHCF(CF₃)₂1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene F15ECF₃CH═CH(CF₂)₄CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-eneF15iE CF₃CH═CH—CF₂CF₂CF(CF₃)₂ 1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-2-ene F15tE CF₃CH═CH—C(CF₃)₂C₂F₅1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hex-2- ene F24EC₂F₅CH═CH(CF₂)₃CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-eneF24iE C₂F₅CH═CHCF₂CF—(CF₃)₂ 1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-3-ene F24sE C₂F₅CH═CHCF(CF₃)—C₂F₅1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5- (trifluoromethyl)hept-3-ene F24tEC₂F₅CH═CHC(CF₃)₃1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3- ene F33EC₂F₅CF₂CH═CH—CF₂C₂F₅1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene F3i3iE(CF₃)₂CFCH═CH—CF(CF₃)₂1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3- ene F33iEC₂F₅CF₂CH═CH—CF(CF₃)₂ 1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept-3-ene F16E CF₃CH═CH(CF₂)₅CF₃1,1,1,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoronon-2-ene F16sECF₃CH═CHCF(CF₃)(CF₂)₂C₂F₅ 1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethyl)hept-2-ene F16tE CF₃CH═CHC(CF₃)₂CF₂C₂F₅1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-ene F25EC₂F₅CH═CH(CF₂)₄CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene F25iEC₂F₅CH═CH—CF₂CF₂CF(CF₃)₂ 1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-3-ene F25tE C₂F₅CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,6,6,7,7,7-decafluoro-5,5- bis(trifluoromethyl)hept-3-ene F34EC₂F₅CF₂CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene F34iEC₂F₅CF₂CH═CH—CF₂CF(CF₃)₂ 1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-4-ene F34sE C₂F₅CF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6- (trifluoromethyl)oct-4-eneF34tE C₂F₅CF₂CH═CH—C(CF₃)₃ 1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)hept-3-ene F3i4E (CF₃)₂CFCH═CH—(CF₂)₃CF₃1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro- 2(trifluoromethyl)oct-3-eneF3i4iE (CF₃)₂CFCH═CH—CF₂CF(CF₃)₂ 1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)hept-3-ene F3i4sE (CF₃)₂CFCH═CH—CF(CF₃)C₂F₅1,1,1,2,5,6,6,7,7,7-decafluoro-2,5- bis(trifluoromethyl)hept-3-eneF3i4tE (CF₃)₂CFCH═CH—C(CF₃)₃1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3- ene F26EC₂F₅CH═CH(CF₂)₅CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-3-ene F26sE C₂F₅CH═CHCF(CF₃)(CF₂)₂C₂F₅1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)non-3-ene F26tE C₂F₅CH═CHC(CF₃)₂CF₂C₂F₅1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5- bis(trifluoromethyl)oct-3-eneF35E C₂F₅CF₂CH═CH—(CF₂)₄CF₃ 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-4-ene F35iE C₂F₅CF₂CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-(trifluoromethyl)non-4-ene F35tE C₂F₅CF₂CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6- bis(trifluoromethyl)oct-4-eneF3i5E (CF₃)₂CFCH═CH—(CF₂)₄CF₃1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-3-ene F3i5iE (CF₃)₂CFCH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7- bis(trifluoromethyl)oct-3-eneF3i5tE (CF₃)₂CFCH═CH—C(CF₃)₂C₂F₅ 1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)hept-3-ene F44E CF₃(CF₂)₃CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10- octadecafluorodec-5-ene F44iECF₃(CF₂)₃CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-4-ene F44sE CF₃(CF₂)₃CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-(trifluoromethyl)non-4-ene F44tE CF₃(CF₂)₃CH═CH—C(CF₃)₃1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,- bis(trifluoromethyl)oct-3-eneF4i4iE (CF₃)₂CFCF₂CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7- bis(trifluoromethyl)oct-4-eneF4i4sE (CF₃)₂CFCF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6- bis(trifluoromethyl)oct-4-eneF4i4tE (CF₃)₂CFCF₂CH═CH—C(CF₃)₃ 1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)hept-3-ene F4s4sE C₂F₅CF(CF₃)CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6- bis(trifluoromethyl)oct-4-eneF4s4tE C₂F₅CF(CF₃)CH═CH—C(CF₃)₃ 1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)hept-3-ene F4t4tE (CF₃)₃CCH═CH—C(CF₃)₃1,1,1,6,6,6-hexafluoro-2,2,5,5- tetrakis(trifluoromethyl)hex-3-ene

Compounds of Formula I may be prepared by contacting a perfluoroalkyliodide of the formula R¹I with a perfluoroalkyltrihydroolefin of theformula R²CH═CH₂ to form a trihydroiodoperfluoroalkane of the formulaR¹CH₂CHIR². This trihydroiodoperfluoroalkane can then bedehydroiodinated to form R¹CH═CHR². Alternatively, the olefin R¹CH═CHR²may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane ofthe formula R¹CHICH₂R² formed in turn by reacting a perfluoroalkyliodide of the formula R²I with a perfluoroalkyltrihydroolefin of theformula R¹CH═CH₂.

Said contacting of a perfluoroalkyl iodide with aperfluoroalkyltrihydroolefin may take place in batch mode by combiningthe reactants in a suitable reaction vessel capable of operating underthe autogenous pressure of the reactants and products at reactiontemperature. Suitable reaction vessels include fabricated from stainlesssteels, in particular of the austenitic type, and the well-known highnickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickelbased alloys and Inconel® nickel-chromium alloys.

Alternatively, the reaction may take be conducted in semi-batch mode inwhich the perfluoroalkyltrihydroolefin reactant is added to theperfluoroalkyl iodide reactant by means of a suitable addition apparatussuch as a pump at the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefinshould be between about 1:1 to about 4:1, preferably from about 1.5:1 to2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1adduct as reported by Jeanneaux, et. al. in Journal of FluorineChemistry, Vol. 4, pages 261-270 (1974).

Preferred temperatures for contacting of said perfluoroalkyl iodide withsaid perfluoroalkyltrihydroolefin are preferably within the range ofabout 150° C. to 300° C., preferably from about 170° C. to about 250°C., and most preferably from about 180° C. to about 230° C.

Suitable contact times for the reaction of the perfluoroalkyl iodidewith the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18hours, preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of theperfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be useddirectly in the dehydroiodination step or may preferably be recoveredand purified by distillation prior to the dehydroiodination step.

The dehydroiodination step is carried out by contacting thetrihydroiodoperfluoroalkane with a basic substance. Suitable basicsubstances include alkali metal hydroxides (e.g., sodium hydroxide orpotassium hydroxide), alkali metal oxide (for example, sodium oxide),alkaline earth metal hydroxides (e.g., calcium hydroxide), alkalineearth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g.,sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, ormixtures of basic substances such as soda lime. Preferred basicsubstances are sodium hydroxide and potassium hydroxide.

Said contacting of the trihydroiodoperfluoroalkane with a basicsubstance may take place in the liquid phase preferably in the presenceof a solvent capable of dissolving at least a portion of both reactants.Solvents suitable for the dehydroiodination step include one or morepolar organic solvents such as alcohols (e.g., methanol, ethanol,n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol),nitriles (e.g., acetonitrile, propionitrile, butyronitrile,benzonitrile, or adiponitrile), dimethyl sulfoxide,N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choiceof solvent may depend on the boiling point product and the ease ofseparation of traces of the solvent from the product duringpurification. Typically, ethanol or isopropanol are good solvents forthe reaction.

Typically, the dehydroiodination reaction may be carried out by additionof one of the reactants (either the basic substance or thetrihydroiodoperfluoroalkane) to the other reactant in a suitablereaction vessel. Said reaction may be fabricated from glass, ceramic, ormetal and is preferably agitated with an impeller or stirring mechanism.

Temperatures suitable for the dehydroiodination reaction are from about10° C. to about 100° C., preferably from about 20° C. to about 70° C.The dehydroiodination reaction may be carried out at ambient pressure orat reduced or elevated pressure. Of note are dehydroiodination reactionsin which the compound of Formula I is distilled out of the reactionvessel as it is formed.

Alternatively, the dehydroiodination reaction may be conducted bycontacting an aqueous solution of said basic substance with a solutionof the trihydroiodoperfluoroalkane in one or more organic solvents oflower polarity such as an alkane (e.g., hexane, heptane, or octane),aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g.,methylene chloride, chloroform, carbon tetrachloride, orperchloroethylene), or ether (e.g., diethyl ether, methyl tert-butylether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane,dimethoxyethane, diglyme, or tetraglyme) in the presence of a phasetransfer catalyst. Suitable phase transfer catalysts include quaternaryammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammoniumhydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammoniumchloride, and tricaprylylmethylammonium chloride), quaternaryphosphonium halides (e.g., triphenylmethylphosphonium bromide andtetraphenylphosphonium chloride), or cyclic polyether compounds known inthe art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction may be conducted in theabsence of solvent by adding the trihydroiodoperfluoroalkane to a solidor liquid basic substance.

Suitable reaction times for the dehydroiodination reactions are fromabout 15 minutes to about six hours or more depending on the solubilityof the reactants. Typically the dehydroiodination reaction is rapid andrequires about 30 minutes to about three hours for completion. Thecompound of formula I may be recovered from the dehydroiodinationreaction mixture by phase separation after addition of water, bydistillation, or by a combination thereof.

In another embodiment of the present invention, fluoroolefins comprisecyclic unsaturated fluorocarbons (cyclo-[CX═CY(CZW)_(n)—] (Formula II),wherein X, Y, Z, and W are independently selected from H and F, and n isan integer from 2 to 5). In one embodiment the fluoroolefins of FormulaII, have at least about 3 carbon atoms in the molecule. In anotherembodiment, the fluoroolefins of Formula II have at least about 4 carbonatoms in the molecule. In yet another embodiment, the fluoroolefins ofFormula II have at least about 5 carbon atoms in the molecule.Representative cyclic fluoroolefins of Formula II are listed in Table 2.

TABLE 2 Cyclic unsaturated fluorocarbons Structure Chemical nameFC-C1316cc cyclo-CF₂CF₂CF═CF— 1,2,3,3,4,4-hexafluorocyclobuteneHFC-C1334cc cyclo-CF₂CF₂CH═CH— 3,3,4,4-tetrafluorocyclobutene HFC-C1436cyclo-CF₂CF₂CF₂CH═CH— 3,3,4,4,5,5,-hexafluorocyclopentene FC-C1418ycyclo-CF₂CF═CFCF₂CF₂— 1,2,3,3,4,4,5,5-octafluorocyclopentene FC-C151-10ycyclo-CF₂CF═CFCF₂CF₂CF₂— 1,2,3,3,4,4,5,5,6,6- decafluorocyclohexene

The compositions of the present invention may comprise a single compoundof Formula I or formula II, for example, one of the compounds in Table 1or Table 2, or may comprise a combination of compounds of Formula I orFormula II.

In another embodiment, fluoroolefins may comprise those compounds listedin Table 3.

TABLE 3 Name Structure Chemical name HFC-1114 (TFE) CF₂═CF₂tetrafluoroethylene HFC-1216 (HFP) CF₃CF═CF₂ hexafluoropropeneHFC-1225ye CF₃CF═CHF 1,2,3,3,3-pentafluoro-1-propene HFC-1225zcCF₃CH═CF₂ 1,1,3,3,3-pentafluoro-1-propene HFC-1225yc CHF₂CF═CF₂1,1,2,3,3-pentafluoro-1-propene HFC-1234ye CHF₂CF═CHF1,2,3,3-tetrafluoro-1-propene HFC-1234yf CF₃CF═CH₂2,3,3,3-tetrafluoro-1-propene HFC-1234ze CF₃CH═CHF1,3,3,3-tetrafluoro-1-propene HFC-1234yc CH₂FCF═CF₂1,1,2,3-tetrafluoro-1-propene HFC-1234zc CHF₂CH═CF₂1,1,3,3-tetrafluoro-1-propene HFC-1243yf CHF₂CF═CH₂2,3,3-trifluoro-1-propene HFC-1243zf CF₃CH═CH₂ 3,3,3-trifluoro-1-propeneHFC-1243yc CH₃CF═CF₂ 1,1,2-trifluoro-1-propene HFC-1243zc CH₂FCH═CF₂1,1,3-trifluoro-1-propene HFC-1243ye CH₂FCF═CHF1,2,3-trifluoro-1-propene HFC-1243ze CHF₂CH═CHF1,3,3-trifluoro-1-propene FC-1318my CF₃CF═CFCF₃1,1,1,2,3,4,4,4-octafluoro-2-butene FC-1318cy CF₃CF₂CF═CF₂1,1,2,3,3,4,4,4-octafluoro-1-butene HFC-1327my CF₃CF═CHCF₃1,1,1,2,4,4,4-heptafluoro-2-butene HFC-1327ye CHF═CFCF₂CF₃1,2,3,3,4,4,4-heptafluoro-1-butene HFC-1327py CHF₂CF═CFCF₃1,1,1,2,3,4,4-heptafluoro-2-butene HFC-1327et (CF₃)₂C═CHF1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1- propene HFC-1327czCF₂═CHCF₂CF₃ 1,1,3,3,4,4,4-heptafluoro-1-butene HFC-1327cye CF₂═CFCHFCF₃1,1,2,3,4,4,4-heptafluoro-1-butene HFC-1327cyc CF₂═CFCF₂CHF₂1,1,2,3,3,4,4-heptafluoro-1-butene HFC-1336yf CF₃CF₂CF═CH₂2,3,3,4,4,4-hexafluoro-1-butene HFC-1336ze CHF═CHCF₂CF₃1,3,3,4,4,4-hexafluoro-1-butene HFC-1336eye CHF═CFCHFCF₃1,2,3,4,4,4-hexafluoro-1-butene HFC-1336eyc CHF═CFCF₂CHF₂1,2,3,3,4,4-hexafluoro-1-butene HFC-1336pyy CHF₂CF═CFCHF₂1,1,2,3,4,4-hexafluoro-2-butene HFC-1336qy CH₂FCF═CFCF₃1,1,1,2,3,4-hexafluoro-2-butene HFC-1336pz CHF₂CH═CFCF₃1,1,1,2,4,4-hexafluoro-2-butene HFC-1336mzy CF₃CH═CFCHF₂1,1,1,3,4,4-hexafluoro-2-butene HFC-1336qc CF₂═CFCF₂CH₂F1,1,2,3,3,4-hexafluoro-1-butene HFC-1336pe CF₂═CFCHFCHF₂1,1,2,3,4,4-hexafluoro-1-butene HFC-1336ft CH₂═C(CF₃)₂3,3,3-trifluoro-2-(trifluoromethyl)-1- propene HFC-1345qz CH₂FCH═CFCF₃1,1,1,2,4-pentafluoro-2-butene HFC-1345mzy CF₃CH═CFCH₂F1,1,1,3,4-pentafluoro-2-butene HFC-1345fz CF₃CF₂CH═CH₂3,3,4,4,4-pentafluoro-1-butene HFC-1345mzz CHF₂CH═CHCF₃1,1,1,4,4-pentafluoro-2-butene HFC-1345sy CH₃CF═CFCF₃1,1,1,2,3-pentafluoro-2-butene HFC-1345fyc CH₂═CFCF₂CHF₂2,3,3,4,4-pentafluoro-1-butene HFC-1345pyz CHF₂CF═CHCHF₂1,1,2,4,4-pentafluoro-2-butene HFC-1345cyc CH₃CF₂CF═CF₂1,1,2,3,3-pentafluoro-1-butene HFC-1345pyy CH₂FCF═CFCHF₂1,1,2,3,4-pentafluoro-2-butene HFC-1345eyc CH₂FCF₂CF═CF₂1,2,3,3,4-pentafluoro-1-butene HFC-1345ctm CF₂═C(CF₃)(CH₃)1,1,3,3,3-pentafluoro-2-methyl-1-propene HFC-1345ftp CH₂═C(CHF₂)(CF₃)2-(difluoromethyl)-3,3,3-trifluoro-1- propene HFC1345fye CH₂═CFCHFCF₃2,3,4,4,4-pentafluoro-1-butene HFC-1345eyf CHF═CFCH₂CF₃1,2,4,4,4-pentafluoro-1-butene HFC-1345eze CHF═CHCHFCF₃1,3,4,4,4-pentafluoro-1-butene HFC-1345ezc CHF═CHCF₂CHF₂1,3,3,4,4-pentafluoro-1-butene HFC-1345eye CHF═CFCHFCHF₂1,2,3,4,4-pentafluoro-1-butene HFC-1354fzc CH₂═CHCF₂CHF₂3,3,4,4-tetrafluoro-1-butene HFC-1354ctp CF₂═C(CHF₂)(CH₃)1,1,3,3-tetrafluoro-2-methyl-1-propene HFC-1354etm CHF═C(CF₃)(CH₃)1,3,3,3-tetrafluoro-2-methyl-1-propene HFC-1354tfp CH₂═C(CHF₂)₂2-(difluoromethyl)-3,3-difluoro-1-propene HFC-1354my CF₃CF═CHCH₃1,1,1,2-tetrafluoro-2-butene HFC-1354mzy CH₃CF═CHCF₃1,1,1,3-tetrafluoro-2-butene FC-141-10myy CF₃CF═CFCF₂CF₃1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene FC-141-10cy CF₂═CFCF₂CF₂CF₃1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene HFC-1429mzt (CF₃)₂C═CHCF₃1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)- 2-butene HFC-1429myzCF₃CF═CHCF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene HFC-1429mzyCF₃CH═CFCF₂CF₃ 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene HFC-1429eycCHF═CFCF₂CF₂CF₃ 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene HFC-1429czcCF₂═CHCF₂CF₂CF₃ 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene HFC-1429cyccCF₂═CFCF₂CF₂CHF₂ 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene HFC-1429pyyCHF₂CF═CFCF₂CF₃ 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene HFC-1429myycCF₃CF═CFCF₂CHF₂ 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene HFC-1429myyeCF₃CF═CFCHFCF₃ 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene HFC-1429eyymCHF═CFCF(CF₃)₂ 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)- 1-buteneHFC-1429cyzm CF₂═CFCH(CF₃)₂ 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene HFC-1429mzt CF₃CH═C(CF₃)₂1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)- 2-butene HFC-1429czymCF₂═CHCF(CF₃)₂ 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)- 1-buteneHFC-1438fy CH₂═CFCF₂CF₂CF₃ 2,3,3,4,4,5,5,5-octafluoro-1-penteneHFC-1438eycc CHF═CFCF₂CF₂CHF₂ 1,2,3,3,4,4,5,5-octafluoro-1-penteneHFC-1438ftmc CH₂═C(CF₃)CF₂CF₃ 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFC-1438czzm CF₂═CHCH(CF₃)₂1,1,4,4,4-pentafluoro-3-(trifluoromethyl)- 1-butene HFC-1438ezymCHF═CHCF(CF₃)₂ 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)- 1-buteneHFC-1438ctmf CF₂═C(CF₃)CH₂CF₃ 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFC-1447fzy (CF₃)₂CFCH═CH₂3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1- butene HFC-1447fzCF₃CF₂CF₂CH═CH₂ 3,3,4,4,5,5,5-heptafluoro-1-pentene HFC-1447fyccCH₂═CFCF₂CF₂CHF₂ 2,3,3,4,4,5,5-heptafluoro-1-pentene HFC-1447czcfCF₂═CHCF₂CH₂CF₃ 1,1,3,3,5,5,5-heptafluoro-1-pentene HFC-1447mytmCF₃CF═C(CF₃)(CH₃) 1,1,1,2,4,4,4-heptafluoro-3-methyl-2- buteneHFC-1447fyz CH₂═CFCH(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene HFC-1447ezz CHF═CHCH(CF₃)₂1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1- butene HFC-1447qztCH₂FCH═C(CF₃)₂ 1,4,4,4-tetrafluoro-2-(trifluoromethyl)-2- buteneHFC-1447syt CH₃CF═C(CF₃)₂ 2,4,4,4-tetrafluoro-2-(trifluoromethyl)-2-butene HFC-1456szt (CF₃)₂C═CHCH₃3-(trifluoromethyl)-4,4,4-trifluoro-2-butene HFC-1456szy CF₃CF₂CF═CHCH₃3,4,4,5,5,5-hexafluoro-2-pentene HFC-1456mstz CF₃C(CH₃)═CHCF₃1,1,1,4,4,4-hexafluoro-2-methyl-2-butene HFC-1456fzce CH₂═CHCF₂CHFCF₃3,3,4,5,5,5-hexafluoro-1-pentene HFC-1456ftmf CH₂═C(CF₃)CH₂CF₃4,4,4-trifluoro-2-(trifluoromethyl)-1-butene FC-151-12c CF₃(CF₂)₃CF═CF₂1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1- hexene (or perfluoro-1-hexene)FC-151-12mcy CF₃CF₂CF═CFCF₂CF₃ 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (or perfluoro-3-hexene) FC-151-12mmtt (CF₃)₂C═C(CF₃)₂1,1,1,4,4,4-hexafluoro-2,3- bis(trifluoromethyl)-2-butene FC-151-12mmzz(CF₃)₂CFCF═CFCF₃ 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene HFC-152- (CF₃)₂C═CHC₂F₅1,1,1,4,4,5,5,5-octafluoro-2- 11mmtz (trifluoromethyl)-2-penteneHFC-152- (CF₃)₂CFCF═CHCF₃ 1,1,1,3,4,5,5,5-octafluoro-4- 11mmyyz(trifluoromethyl)-2-pentene PFBE CF₃CF₂CF₂CF₂CH═CH₂3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (or (or HFC-1549fz)perfluorobutylethylene) HFC-1549fztmm CH₂═CHC(CF₃)₃4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1- butene HFC-1549mmtts(CF₃)₂C═C(CH₃)(CF₃) 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene HFC-1549fycz CH₂═CFCF₂CH(CF₃)₂2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)- 1-pentene HFC-1549mytsCF₃CF═C(CH₃)CF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2- penteneHFC-1549mzzz CF₃CH═CHCH(CF₃)₂1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)- 2-pentene HFC-1558szyCF₃CF₂CF₂CF═CHCH₃ 3,4,4,5,5,6,6,6-octafluoro-2-hexene HFC-1558fzcccCH₂═CHCF₂CF₂CF₂CHF₂ 3,3,4,4,5,5,6,6-octafluoro-2-hexene HFC-1558mmtzc(CF₃)₂C═CHCF₂CH₃ 1,1,1,4,4-pentafluoro-2-(trifluoromethyl)- 2-penteneHFC-1558ftmf CH₂═C(CF₃)CH₂C₂F₅4,4,5,5,5-pentafluoro-2-(trifluoromethyl)- 1-pentene HFC-1567ftsCF₃CF₂CF₂C(CH₃)═CH₂ 3,3,4,4,5,5,5-heptafluoro-2-methyl-1- penteneHFC-1567szz CF₃CF₂CF₂CH═CHCH₃ 4,4,5,5,6,6,6-heptafluoro-2-hexeneHFC-1567fzfc CH₂═CHCH₂CF₂C₂F₅ 4,4,5,5,6,6,6-heptafluoro-1-hexeneHFC-1567sfyy CF₃CF₂CF═CFC₂H₅ 1,1,1,2,2,3,4-heptafluoro-3-hexeneHFC-1567fzfy CH₂═CHCH₂CF(CF₃)₂4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1- pentene HFC-CF₃CF═CHCH(CF₃)(CH₃) 1,1,1,2,5,5,5-heptafluoro-4-methyl-2- 1567myzzmpentene HFC-1567mmtyf (CF₃)₂C═CFC₂H₅1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2- pentene FC-161-14myyCF₃CF═CFCF₂CF₂C₂F₅ 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene FC-161-14mcyy CF₃CF₂CF═CFCF₂C₂F₅1,1,1,2,2,3,4,5,5,6,6,7,7,7- tetradecafluoro-2-heptene HFC-162-13mzyCF₃CH═CFCF₂CF₂C₂F₅ 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2- hepteneHFC162-13myz CF₃CF═CHCF₂CF₂C₂F₅1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2- heptene HFC-162-CF₃CF₂CH═CFCF₂C₂F₅ 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3- 13mczyheptene HFC-162- CF₃CF₂CF═CHCF₂C₂F₅1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3- 13mcyz heptene

The compounds listed in Table 2 and Table 3 are available commerciallyor may be prepared by processes known in the art or as described herein.

1,1,1,4,4-pentafluoro-2-butene may be prepared from1,1,1,2,4,4-hexafluorobutane (CHF₂CH₂CHFCF₃) by dehydrofluorination oversolid KOH in the vapor phase at room temperature. The synthesis of1,1,1,2,4,4-hexafluorobutane is described in U.S. Pat. No. 6,066,768,incorporated herein by reference.

1,1,1,4,4,4-hexafluoro-2-butene may be prepared from1,1,1,4,4,4-hexafluoro-2-iodobutane (CF₃CHICH₂CF₃) by reaction with KOHusing a phase transfer catalyst at about 60° C. The synthesis of1,1,1,4,4,4-hexafluoro-2-iodobutane may be carried out by reaction ofperfluoromethyl iodide (CF₃I) and 3,3,3-trifluoropropene (CF₃CH═CH₂) atabout 200° C. under autogenous pressure for about 8 hours.

3,4,4,5,5,5-hexafluoro-2-pentene may be prepared by dehydrofluorinationof 1,1,1,2,2,3,3-heptafluoropentane (CF₃CF₂CF₂CH₂CH₃) using solid KOH orover a carbon catalyst at 200-300° C. 1,1,1,2,2,3,3-heptafluoropentanemay be prepared by hydrogenation of 3,3,4,4,5,5,5-heptafluoro-1-pentene(CF₃CF₂CF₂CH═CH₂).

1,1,1,2,3,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,2,3,3,4-heptafluorobutane (CH₂FCF₂CHFCF₃) using solid KOH.

1,1,1,2,4,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,2,2,4,4-heptafluorobutane (CHF₂CH₂CF₂CF₃) using solid KOH.

1,1,1,3,4,4-hexafluoro2-butene may be prepared by dehydrofluorination of1,1,1,3,3,4,4-heptafluorobutane (CF₃CH₂CF₂CHF₂) using solid KOH.

1,1,1,2,4-pentafluoro-2-butene may be prepared by dehydrofluorination of1,1,1,2,2,3-hexafluorobutane (CH₂FCH₂CF₂CF₃) using solid KOH.

1,1,1,3,4-pentafluoro-2-butene may be prepared by dehydrofluorination of1,1,1,3,3,4-hexafluorobutane (CF₃CH₂CF₂CH₂F) using solid KOH.

1,1,1,3-tetrafluoro-2-butene may be prepared by reacting1,1,1,3,3-pentafluorobutane (CF₃CH₂CF₂CH₃) with aqueous KOH at 120° C.

1,1,1,4,4,5,5,5-octafluoro-2-pentene may be prepared from(CF₃CHICH₂CF₂CF₃) by reaction with KOH using a phase transfer catalystat about 60° C. The synthesis of4-iodo-1,1,1,2,2,5,5,5-octafluoropentane may be carried out by reactionof perfluoroethyliodide (CF₃CF₂I) and 3,3,3-trifluoropropene at about200° C. under autogenous pressure for about 8 hours.

1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared from1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane (CF₃CF₂CHICH₂CF₂CF₃) byreaction with KOH using a phase transfer catalyst at about 60° C. Thesynthesis of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane may be carriedout by reaction of perfluoroethyliodide (CF₃CF₂I) and3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂) at about 200° C. underautogenous pressure for about 8 hours.

1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene may be preparedby the dehydrofluorination of1,1,1,2,5,5,5-heptafluoro-4-iodo-2-(trifluoromethyl)-pentane(CF₃CHICH₂CF(CF₃)₂) with KOH in isopropanol. CF₃CHICH₂CF(CF₃)₂ is madefrom reaction of (CF₃)₂CFI with CF₃CH═CH₂ at high temperature, such asabout 200° C.

1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene may be prepared by the reactionof 1,1,1,4,4,4-hexafluoro-2-butene (CF₃CH═CHCF₃) withtetrafluoroethylene (CF₂═CF₂) and antimony pentafluoride (SbF₅).

2,3,3,4,4-pentafluoro-1-butene may be prepared by dehydrofluorination of1,1,2,2,3,3-hexafluorobutane over fluorided alumina at elevatedtemperature.

2,3,3,4,4,5,5,5-ocatafluoro-1-pentene may be prepared bydehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over solidKOH.

1,2,3,3,4,4,5,5-octafluoro-1-pentene may be prepared bydehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane overfluorided alumina at elevated temperature.

Many of the compounds of Formula I, Formula II, Table 1, Table 2, andTable 3 exist as different configurational isomers or stereoisomers.When the specific isomer is not designated, the present invention isintended to include all single configurational isomers, singlestereoisomers, or any combination thereof. For instance, F11E is meantto represent the E-isomer, Z-isomer, or any combination or mixture ofboth isomers in any ratio. As another example, HFC-1225ye is meant torepresent the E-isomer, Z-isomer, or any combination or mixture of bothisomers in any ratio.

In certain embodiments, in the composition comprising HF, at least onefluoroolefin, and at least one extractant, the at least one fluoroolefincomprises a fluoropropene. In one embodiment, the fluoroolefin isZ-HFC-1225ye, E-HFC-1225ye, or any combination or mixture of bothisomers in any ratio. In another embodiment, the fluoroolefin isHFC-1234yf. In another embodiment, the fluoroolefin is Z-HFC-1234ze,E-HFC-1234ze, or any combination or mixture of both isomers in anyratio.

In one embodiment, the extractant may be any compound that would beeffective in separation of fluoroolefins from mixtures comprising HF andfluoroolefin in an extraction process. In another embodiment,extractants may be selected from the group consisting of hydrocarbons,chlorocarbons, chlorofluorocarbons, hydrofluorocarbons,hydrochlorofluorocarbons, perfluorocarbons, and perfluorinated ethers.

In one embodiment, hydrocarbon extractants comprise compounds containing2 to 12 carbon atoms and hydrogen. Hydrocarbon extractants may belinear, branched, cyclic, saturated or unsaturated compounds.Representative hydrocarbon extractants include but are not limited toethane, ethylene, n-propane propylene, n-butane, isobutane, cyclobutane,1-butene, 2-butene (cis and trans), n-pentane, isopentane(2-methylbutane), neopentane (2,2-dimethylpropane), cyclopentane,1-pentene, 2-pentene (cis and trans), cyclopentene, n-hexane,cyclohexane, 2-methylpentane, 3-methylpentane, 1-hexene, 2-hexene (cisand trans), 3-hexene (cis and trans), neohexane (2,2-dimethylbutane),neohexene (3,3-dimethyl-1-butene), 2,2-dimethylbutane,2,3-dimethylbutane, 2,3-dimethyl-2-butene, 2,3-dimethyl-1-butene,3,3-dimethyl-1-butene, n-heptane, 1-heptene, 2-heptene (cis and trans),3-heptene (cis and trans), cycloheptene, octane (all isomers), nonane(all isomers), decane (all isomers), undecane (all isomers), dodecane(all isomers), benzene, toluene, and mixtures thereof.

In another embodiment, chlorocarbon extractants comprise compounds withcarbon, chlorine and optionally hydrogen. Representative chlorocarbonsinclude but are not limited to tetrachloroethylene, trichloroethylene,1,1-dichloroethylene, 1,2-dichloroethylene, carbon tetrachloride(tetrachloromethane), chloroform (trichloromethane), methylene chloride(dichloromethane), 1,1,2,2-tetrachloroethane, 1,1,1,2-tetrachloroethane,1,1,2-trichloroethane, 1,1,1-trichloroethane,1,1,1,3,3,3-hexachloropropane and mixtures thereof.

In another embodiment, chlorofluorocarbon (CFC) extractants comprisecompounds with carbon, chlorine and fluorine. Representative CFCsinclude but are not limited to dichlorodifluoromethane (CFC-12),fluorotrichloromethane (CFC-11), fluoropentachloroethane (CFC-111),1,2-difluoro-1,1,2,2-tetrachloroethane (CFC-112),1,1-difluoro-1,2,2,2-tetrachloroethane (CFC-112a),1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113),1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a),1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114),1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a),chloropentafluoroethane (CFC-115),1,1,1,2,3-pentafluoro-2,3,3-trichloropropane (CFC-215bb),2,2-dichloro-1,1,1,3,3,3-hexafluoropropane (CFC-216aa),2,3-dichloro-1,1,1,2,3,3-hexafluoropropane (CFC-216ba), and2-chloro-1,1,1,2,3,3,3-heptafluoropropane (CFC-217ba), and mixturesthereof.

In another embodiment, hydrochlorofluorocarbon (HCFC) extractantscomprise compounds with carbon, chlorine, fluorine and hydrogen.Representative HCFCs include but are not limited todichlorofluoromethane (HCFC-21), 1,1,2-trichloro-2,2-difluoroethane(HCFC-122), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123),1,2-dichloro-1,1,1-trifluoroethane (HCFC-123a),2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124),1-chloro-1,1,2,2-tetrafluoroethane (HCFC-124a),1-chloro-1,2,2-trifluoroethane (HCFC-133),2-chloro-1,1,1-trifluoroethane (HCFC-133a), 1,1-dichloro-2-fluoroethane(HCFC-141a), 1,1-dichloro-1-fluoroethane (HCFC-141b),1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-1,1-difluoroethane(HCFC-142b), and mixtures thereof.

Hydrofluorocarbon (HFC) extractants comprise compounds that containcarbon, hydrogen and fluorine, and may be saturated or unsaturated (thusincluding fluoroolefins). Representative HFCs include but are notlimited to 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane(HFC-63-14mcee), 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene,1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (HFC-162-13mczy),fluorobenzene, 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane(HFC-63-14mcee), 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, HFC-162-13mczy,1,2,3,3,3-pentafluoro-1-propene (HFC-1225ye),1,1,3,3,3-pentafluoro-1-propene (HFC-1225zc),1,3,3,3-tetrafluoro-1-propene (HFC-1234ze),2,3,3,3-tetrafluoro-1-propene (HFC-1234yf, 3,3,3-trifluoro-1-propene(HFC-1243zf), 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429myz),1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429mzy),1,1,1,4,4,4-hexafluoro-2-butene (F11E),1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E),1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluoro-3-octene (F24E),1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluoro-4-octene (F33E), andmixtures thereof.

Perfluorocarbon (PFC) extractants comprise compounds with carbon andfluorine only. Representative PFCs include but are not limited tooctafluoropropane (PFC-218), octafluorocyclobutane (PFC-C318), allisomers of C₄F₁₀ (PFC-31-10), hexafluoropropylene (HFP, PFC-1216), allisomers of C₅F₁₂ (PFC-41-12), all isomers of C₆F₁₄ (PFC-51-14) andmixtures thereof.

Perfluorinated ether extractants include but are not limited to PMVE(perfluoromethylvinyl ether) and PEVE (perfluoroethylvinyl ether.

Extractants as described above are available commercially or may beproduced by methods known in the art.

The weight ratio of the HF, fluoroolefin, and extractant in thecomposition present in the extractor will depend upon the means ofproducing the composition and the efficiency of the extraction. In oneembodiment, the HF may be from about 5 weight percent to about 15 weightpercent of the composition; the fluoroolefin may be from about 30 weightpercent to about 80 weight percent and the extractant may be from about5 to about 70 weight percent.

In another embodiment, the HF may be from about 5 weight percent toabout 15 weight percent; the fluoroolefin may be from about 40 weightpercent to about 75 weight percent; and the extractant may be from about10 weight percent to about 60 weight percent.

In one embodiment, the compositions comprising HF, fluoroolefin andextractant may be prepared by any convenient method to combine thedesired amounts of the individual components. One method is to weigh thedesired component amounts and thereafter combine the components in anappropriate vessel. Agitation may be used, if desired.

Alternatively, the compositions comprising HF and fluoroolefin may beprepared by feeding the effluent from a dehydrofluorination reactor thatcontains HF and fluoroolefin to the extractor. The extractant may beadded at a separate feed point such that the composition comprising HF,fluoroolefin, and extractant is formed directly in the extractor. Mixingmay be accomplished by any usual means, or mixing may be accomplished byfeeding the lower density phase (HF/fluoroolefin phase or extractantphase) to the extractor at a point lower than the higher density phasesuch that the lower density phase will rise through the higher densityphase resulting in a mixed composition.

The compositions as described above may be representative of thecontents of the extractor in the separation process to be describedbelow. The composition may be different at different points in theextractor.

3. Separation Processes

In one embodiment, the process for separating fluoroolefin from acomposition of HF and fluoroolefin may be accomplished by feeding acomposition comprising HF and fluoroolefin to an extractor. Thecomposition comprising HF and fluoroolefin may be prepared by any usualmethod. In one embodiment a composition comprising reactor effluent froma dehydrofluorination reactor will contain a 50/50 mole percentcomposition of HF and fluoroolefin (eg., 13.2 weight percent HF and 86.8weight percent fluoroolefin for HF/HFC-1225ye product ofdehydrofluorination).

In certain embodiments, in the process of purifying fluoroolefin from acomposition comprising HF and fluoroolefin, the fluoroolefin comprises afluoropropene. In one embodiment, the fluoroolefin is Z-HFC-1225ye,E-HFC-1225ye, or any combination or mixture of both isomers in anyratio. In another embodiment, the fluoroolefin is HFC-1234yf. In anotherembodiment, the fluoroolefin is Z-HFC-1234ze, E-HFC-1234ze, or anycombination or mixture of both isomers in any ratio.

In one embodiment, the process for separating fluoroolefin from amixture of HF and fluoroolefin comprises feeding the compositioncomprising HF and fluoroolefin and a composition comprising extractantto an extractor. In one embodiment, the extractor may be anyconventional liquid-liquid extraction device, for example a staticmixer, a stirred vessel, a mixer/settler, a rotary-disc extractor, anextractor with centrifugation or a column with perforated plates orpacking.

In one embodiment, the extractor may operate counter-currently, meaningthat the extractant and the composition comprising HF and fluoroolefinflow in opposite directions. In another embodiment, the extractor mayoperate co-currently, meaning that the extractant and the compositioncomprising HF and fluoroolefin flow in the same direction.

In one embodiment, the extraction may be carried out in a continuousmanner. In another embodiment, the extraction may be carried out in abatch-wise manner.

In some embodiments, the temperature at which the extraction may becarried out depends upon the extractant being used and the fluoroolefinproduct. In general the lower the boiling point of the extractant thelower the operating temperature and/or the higher the operating pressurethat may be required to maintain the composition comprising HF,fluoroolefin and extractant in the liquid state. In one embodiment, theextractor may typically be operated from about −50° C. to about 150° C.In another embodiment the extractor may be operated from about −25° C.to about 100° C. In yet another embodiment the extractor may be operatedfrom about −15° C. to about 40° C.

In one embodiment, the extractor may typically be operated from about14.7 psia (101.3 kPa) to about 300 psia (2069 kPa). In anotherembodiment, the extractor may be operated from about 30 psia (206.9 kPa)to about 200 psia (1379 kPa). In one other embodiment the extractor maybe operated from about 50 psia (345 kPa) to about 150 psia (1034 kPa).In yet another embodiment, pressure in the extractor may be adjusted byaddition of an inert gas. Any gaseous substance, which does not reactsubstantially under the extraction conditions, such as nitrogen,hydrogen chloride, argon or a mixture thereof, may be used as an inertgas.

In one embodiment, the HF/fluoroolefin composition may be of higherdensity than the extractant, thus the extractant may be fed to a pointin the extractor below the feed point of the HF/fluoroolefin composition(as illustrated in FIG. 1). In another embodiment, the HF/fluoroolefincomposition may be of lower density than the extractant, thus theextractant may be fed to a point in the extractor above the feed pointof the HF/fluoroolefin composition (as illustrated in FIG. 2).

In certain embodiments (e.g., as illustrated in FIG. 1 and FIG. 2),extractant-rich phase may be removed from the extractor as an extract,comprising extractant and fluoroolefin. The extract may be fed to anextractant recovery column for the recovery of fluoroolefin productessentially free of extractant. In one embodiment, the fluoroolefin istaken off the top of the extractant recovery column. The fluoroolefinproduct may still contain some minor amount of HF and extractant, whichcan be removed by any conventional method known in the art, such asaqueous (e.g. caustic) scrubbing or non-aqueous (e.g. alumina, activecharcoal or zeolite bed) methods.

In one embodiment, the extractant is removed from the bottom of theextractant recovery column and may be recycled back to the extractor.

In one embodiment, the composition exiting the top of the extractantrecovery column comprising fluoroolefin may be condensed usingconventional reflux condensers. At least a portion of this condensedstream may be returned to the top of the column as reflux. The ratio ofthe condensed material, which is returned to the top of the extractrecovery column as reflux, to the material removed from the top of theextract recovery column is commonly referred to as the reflux ratio.

The specific conditions, which may be used for operating the extractantrecovery column depend upon a number of parameters, such as the physicalproperties of the extractant used, the diameter of the distillationcolumn, feed points, and the number of separation stages in the column,among others.

The pressures and temperatures required in the extractant recoverycolumn to provide the separations desired will vary depending upon thefluoroolefin being recovered and the extractant being used as well. Inone embodiment the extractant recovery column may be operated at apressure range from about 14.7 psia (101.3 kPa) to about 300 psia(2068.5 kPa) with a top temperature range from about −50° C. to about100° C. and a bottom temperature range from about 50° C. to about 250°C. In another embodiment the extractant recovery column may be operatedfrom about 50 psia (345 kPa) to about 150 psia (1034 kPa) with a toptemperature of about 30° C. to about 75° C. and a bottom temperaturefrom about 75° C. to about 175° C.

An HF-rich phase may be removed from the extractor as a raffinate,comprising HF with minor amounts of extractant and fluoroolefin. Thisrecovered HF may be used as is in any usual manner of using HF (e.g.other chemical manufacturing processes). Alternatively, the raffinatemay be fed to a raffinate stripping column for the recovery of HFproduct essentially free of fluoroolefin and extractant. In oneembodiment, the HF product is taken off the bottom of the raffinatestripping column. Such HF product may be used in any manner for which HFis found useful. For instance, HF is useful in fluorination ofhydrocarbons or chlorocarbons to produce hydrochlorofluorocarbons orhydrofluorocarbons.

In one embodiment, a second extractant-rich phase with minor amounts ofHF and fluoroolefin may be removed from the top of the raffinatestripping column. The second extractant-rich phase may be furtherpurified using a decanter that allows phase separation of extractant andHF. In the decanter, the second extractant-rich phase separates into thedecanter extractant-rich phase and the decanter HF-rich phase with thelower density phase being the top phase and the higher density phasebeing the bottom phase. The decanter extractant-rich phase may berecycled back to the extractor while the decanter HF-rich phase mayreturn to the raffinate stripping column as reflux. Residualfluoroolefin present in the second extractant-rich phase will return tothe extractor with the extractant.

In one embodiment the raffinate stripping column may be operated at apressure range from about 14.7 psia (101.3 kPa) to about 100 psia (689.5kPa) with a top temperature range from about −50° C. to about 90° C. anda bottom temperature range from about 20° C. to about 100° C. In anotherembodiment the extractant recovery column may be operated from about 50psia (345 kPa) to about 75 psia (517 kPa) with a top temperature ofabout 50° C. to about 70° C. and a bottom temperature from about 50° C.to about 70° C.

In one embodiment, as may be seen in the above description, extractantmay be recycled to the extractor from both the extractant recoverycolumn and the raffinate stripping column. Even so, there may be a needto provide make-up flow of the extractant to maintain the optimal feedof extractant to the extractor due to common process losses. In oneembodiment, the recycle from the extractant recovery column, raffinatestripping column and any required make-up extractant may be fed to acommon mixer prior to the feed line to the extractor.

Referring to FIG. 1, the process may be described as follows. Thecomposition comprising HF and fluoroolefin (100) is fed to the extractor(110). The extractant (270) is also fed to the extractor. In general,the lower density composition is fed to a lower point in the extractorto encourage mixing. The raffinate (130) is taken out of the bottom ofthe extractor to a raffinate stripping column (140). The top stream fromthe raffinate stripping column (150) is condensed, cooled and fed to adecanter (160) in which tow liquid phases are formed. The HF rich phase(170) from the decanter is sent back to the raffinate stripping column(140) as reflux. The extractant rich phase from the decanter (180) isrecycled back to the extractor (110) via a mixer (260). The bottomstream from the raffinate stripping column (190) is recovered as HFessentially free of fluoroolefin and extractant.

The extract (120) from the extractor (110) is fed to an extractantrecovery column (200). The extractant recovery column bottom (240),containing essentially all of the extraction in the column feed, isrecycled back to the extractor via the mixer (260). The top stream fromthe extractant recovery column (210) is partially or completelycondensed with a portion of condensate returned to the extractantrecovery column as reflux (220). The remainder of the stream (210) isrecovered as the fluoroolefin product (230), essentially free ofextractant.

Referring to FIG. 2, the process may be described as follows. Thecomposition comprising HF and fluoroolefin (100) is fed to the extractor(110). The extractant (270) is also fed to the extractor. The raffinate(130) is taken off the top of the extractor to a raffinate strippingcolumn (140). The top stream from the raffinate stripping column (150)is condensed, cooled and fed to a decanter (160) in which two liquidphases are formed. The extractant rich phase from the decanter (180) isrecycled back to the extractor via a mixer (260). The HF rich phase fromthe decanter (170) is recycled back to the raffinate stripping column asreflux. The bottom stream of the raffinate stripping column (190) isremoved as HF essentially free of fluoroolefin and extractant.

The extract (120) from the bottom of the extractor is fed to anextractant recovery column (200). The bottom of the extractant recoverycolumn (240) is recycled back to the extractor via the mixer (260). Thetop stream from the extractant recovery column (210) is partially orcompletely condensed with a portion of condensate returned to theextractant recovery column as reflux (220). The remainder of the stream(210) is recovered as the fluoroolefin product (230), essentially freeof extractant.

The process equipment for all the processes disclosed herein and theassociated feed lines, effluent lines and associated units may beconstructed of materials resistant to hydrogen fluoride. Typicalmaterials of construction, well-known to the art, include stainlesssteels, in particular of the austenitic type, and the well-known highnickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickelbased alloys and Inconel® nickel-chromium alloys.

While not illustrated in the figures, it is understood that certainpieces of process equipment may be used in the processes describedherein, for optimization. For instance, pumps, heat exchangers, such asheaters or coolers, or other conventional equipment may be used whereappropriate. As an example, it is desirable to have the feed to adistillation column at the same temperature as the point in the columnthat it is fed. Therefore, heating or cooling of the process stream maybe necessary to match the temperature.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Example 1

HFC-1225zc (1,1,1,3,3-pentafluoropropene) and HF form an azeotrope asdisclosed in U.S. Patent Application Publication No. 2006/0116538 A1.Therefore, separation of HF from HFC-1225zc is not possible byconventional distillation. Example 1 demonstrates that HFC-1225zc may beseparated from HF by liquid-liquid extraction using n-hexane as theextractant. A composition comprising 50/50 mole percent HF andHFC-1225zc is fed to the top of an extractor at 1000 lbs/hour (454kg/hour). N-hexane (extractant) is fed to the bottom of the extractor at500 lbs/hour (227 kg/hour). The data in Table 4 were calculated usingmeasured thermodynamic properties.

TABLE 4 HF/HFC- HFC-1225zc HF Component or 1225zc feed product productvariable (100) Extract (120) Raffinate (130) (230) (190) HF, wt % 13.20.44 98.0 0.69 100 HFC-1225zc, 86.8 63.3 0.03 99.3 1 ppm wt % n-hexane,wt % 0 36.3 1.97 1 ppm 6 ppm Temp, ° C. 30.0 30.0 30.0 16.4 67.2 Pres,psia (kPa) 164.7 (1136) 94.7 (653) 94.7 (653) 64.7 (446) 65.7 (453.0)The above data is calculated for an extractor with 6 theoretical stagesoperating at a temperature of 30° C. The extractant recovery column has20 theoretical stages (the extract is fed on the 8^(th) stage from thebottom), operating at a top pressure of 50 psig and a reflux flow of1300 lb/hour. The raffinate stripping column has 5 theoretical stages(raffinate fed on the second stage from the bottom), operating at a toppressure of 50 psig and a reflux flow of 75 lb/hour. The decanteroperates at a temperature of 0° C.

Example 2

Z-HFC-1225ye (Z-1,1,1,2,3-pentafluoropropene) and HF form an azeotropeas disclosed in U.S. Patent Application Publication No. 2007/0100174 A1.Therefore, separation of HF from Z-HFC-1225ye is not possible byconventional distillation. Example 2 demonstrates that Z-HFC-1225ye maybe separated from HF by liquid-liquid extraction using1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) as the extractant. Acomposition comprising 50/50 mole percent HF and Z-HFC-1225ye is fed tothe bottom of an extractor at a rate of 1000 lbs/hour (454 kg/hour).CFC-113 (extractant) is fed to the bottom of the extractor at a rate of800 lbs/hour (363 kg/hour). The data in Table 5 were calculated usingmeasured thermodynamic properties.

TABLE 5 Z-HFC- HF/Z-HFC- 1225ye HF Component or 1225ye feed ExtractRaffinate product product variable (100) (120) (130) (230) (190) HF, wt% 13.2 0.7 92.1 1.3 100 Z-HFC-1225ye, 86.8 52.0 200 ppm 98.7 <1 ppm wt %CFC-113, wt % 0 47.3 7.9 10 ppm   5 ppm Temp, ° C. 30.0 25.0 25.0 25.267.2 Pres, psia (kPa) 164.7 (1135.6) 84.7 (584.0) 84.7 (584.0) 84.7(584.0) 65.7 (453)The above data is calculated for an extractor with 6 theoretical stagesoperating at a temperature of 25° C. The extractant recovery column has20 theoretical stages, the extract is fed on the 5^(th) stage from thebottom, and the column operates with a top pressure of 70 psig with 900lbs/hour reflux. The raffinate stripping column has 5 theoreticalstages, the raffinate is fed to the second stage from the top, and thecolumn operates with a top pressure of 50 psig. The decanter operates ata temperature of 30° C.

Example 3

HFP (hexafluoropropene or PFC-1216) and HF form an azeotrope asdisclosed in U.S. Pat. No. 6,407,297. Therefore, separation of HF fromHFP is not possible by conventional distillation. Example 3 demonstratesthat HFP may be separated from HF by liquid-liquid extraction usingtetrachloroethylene (perchloroethylene or PCE) as the extractant. Acomposition comprising 50/50 mole percent HF and HFP is fed to thebottom of an extractor at a rate of 1000 lbs/hour (454 kg/hour). PCE(extractant) is fed to the top of the extractor at a rate of 800lbs/hour (363 kg/hour). The data in Table 6 were calculated usingmeasured thermodynamic properties.

TABLE 6 HF Component or HF/HFP feed Extract Raffinate HFP productproduct variable (100) (120) (130) (230) (190) HF, wt % 11.8 0.35 97.30.66 100 HFP, wt % 88.2 52.3 1.6 99.34 <1 ppm PCE, wt % 0 47.3 1.1 <1ppm 10 ppm Temp, ° C. 30.0 30.0 30.0 −11.0 95.4 Pres, psia (kPa) 164.7(1135.6) 144.7 (998) 144.7 (998) 34.7 (239) 135.7 (936)The above data is calculated for an extractor with 6 theoretical stagesoperating at a temperature of 30° C. and pressure of 130 psig. Theextractant recovery column has 10 theoretical stages, the extract is fedin the middle of the column, and the column operates with a top pressureof 20 psig with 300 lbs/hour reflux. The raffinate stripping column has10 theoretical stages, the raffinate is fed to the second stage from thetop, and the column operates with a top pressure of 120 psig. Thedecanter operates at a temperature of 30° C.

Example 4

It is known that tetrafluoroethylene (PFC-1114 or TFE) and HF form anazeotrope. Therefore, separation of HF from TFE is not possible byconventional distillation. Example 4 demonstrates that TFE may beseparated from HF by liquid-liquid extraction using octafluoropropane(PFC-218) as the extractant. A composition comprising 50/50 mole percentHF and TFE is fed to the bottom of an extractor at a rate of 1000lbs/hour (454 kg/hour). PFC-218 (extractant) is fed to the top of theextractor at a rate of 200 lbs/hour (90.7 kg/hour). The data in Table 7were calculated using measured thermodynamic properties.

TABLE 7 HF Component or HF/TFE feed Extract Raffinate TFE productproduct variable (100) (120) (130) (230) (190) HF, wt % 16.7 0.93 82.31.1 100 TFE, wt % 83.3 82.1 3.3 98.9 <1 ppm PFC-218, wt % 0 17.0 14.4 10ppm <1 ppm Temp, ° C. −30.0 −40.0 −40.0 −32.9 67.2 Pres, psia 164.7(1135.6) 104.7 (722) 104.7 (722) 94.7 (653) 65.7 (453) (kPa)The above data is calculated for an extractor with 4 theoretical stagesoperating at a temperature of −40° C. and pressure of 90 psig. Theextractant recovery column has 20 theoretical stages, the extract is tothe 6^(th) stage from the bottom of the column, and the column operateswith a top pressure of 80 psig with 1000 lbs/hour reflux. The raffinatestripping column has 5 theoretical stages, the raffinate is fed to thetop stage, and the column operates with a top pressure of 50 psig. Thedecanter operates at a temperature of 40° C.

Example 5

HFC-1234yf (2,3,3,3-tetrafluoro-1-propene) and HF form an azeotrope asdisclosed in U.S. Patent Application Publication No. 2007/0100175 A1.Therefore, separation of HF from HFC-1234yf is not possible byconventional distillation. Example 5 demonstrates that HFC-1234yf may beseparated from HF by liquid-liquid extraction using Z-HFC-1225ye(Z-1,2,3,3,3-pentafluoro-1-propene) as the extractant. A compositioncomprising 50/50 mole percent HF and HFC-1234yf is fed to the bottom ofan extractor at a rate of 1000 lbs/hour (454 kg/hour). Z-HFC-1225ye(extractant) is fed to the top of the extractor at a rate of 1000lbs/hour (454 kg/hour). The data in Table 8 were calculated usingmeasured thermodynamic properties.

TABLE 8 HF/HFC- HFC-1234yf HF Component or 1234yf feed product productvariable (100) Extract (120) Raffinate (130) (230) (190) HF, wt % 14.90.39 8.88 0.49 100 HFC-1234yf, 85.1 82.5 46.7 99.5  2 ppm wt % Z-HFC- 017.1 44.4 130 ppm 10 ppm 1225ye, wt % Temp, ° C. −30 −40 −40 −13.5 67.2Pres, psia (kPa) 164.7 (1136) 84.7 (584.0) 84.7 (584.0) 29.7 (205) 65.7(453)The above data is calculated for an extractor with 8 theoretical stagesoperating at a temperature of −40° C. and pressure of 70 psig. Theextractant recovery column has 50 theoretical stages, the extract is fedto the 7^(th) stage from the bottom of the column, and the columnoperates with a top pressure of 15 psig with 5000 lbs/hour reflux. Theraffinate stripping column has 7 theoretical stages, the raffinate isfed to the top stage, and the column operates with a top pressure of 50psig. The decanter operates at a temperature of −40° C.

Example 6

Example 6 demonstrates that TFE may be separated from HF byliquid-liquid extraction using PMVE (perfluoromethylvinyl ether) as theextractant. A composition comprising 50/50 mole percent HF and TFE isfed to the bottom of an extractor at a rate of 1000 lbs/hour (454kg/hour). PMVE (extractant) is fed to the top of the extractor at a rateof 500 lbs/hour (227 kg/hour). The data in Table 9 were calculated usingmeasured thermodynamic properties.

TABLE 9 HF Component or HF/TFE feed TFE product product variable (100)Extract (120) Raffinate (130) (230) (190) HF, wt % 16.7 0.54 71.5 0.82100 TFE, wt % 83.3 65.0 2.3 99.2 <1 ppm PMVE, wt % 0 34.4 26.2 10 ppm <1ppm Temp, ° C. −20.0 −30.0 −30.0 −32.8 67.2 Pres, psia (kPa) 114.7 (791)109.7 (756) 109.7 (756) 94.7 (653) 65.7 (453)The above data is calculated for an extractor with 6 theoretical stagesoperating at a temperature of −30° C. and pressure of 95 psig. Theextractant recovery column has 20 theoretical stages, the extract is fedto the 6^(th) stage from the bottom of the column, and the columnoperates with a top pressure of 80 psig with 1000 lbs/hour reflux. Theraffinate stripping column has 5 theoretical stages, the raffinate isfed to the top stage, and the column operates with a top pressure of 50psig. The decanter operates at a temperature of −30° C.

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any sub-combination.Further, reference to values stated in ranges include each and everyvalue within that range.

1. A process for separating fluoroolefin from a composition comprisingHF and fluoroolefin, said process comprising extracting said compositionwith an extractant, wherein said extractant comprises at least onecompound selected from the group consisting of hydrocarbons,chlorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons,hydrofluorocarbons, perfluorocarbons, and perfluorinated ethers, andwherein said fluoroolefin is separated from said mixture by saidextractant, and wherein said fluoroolefin comprises compounds with 3 to10 carbon atoms and is selected from the group consisting of: (i)fluoroolefins of the formula E- or Z—R1CH═CHR2, wherein R1 and R2 are,independently, C1 to C6 perfluoroalkyl groups; (ii) cyclic fluoroolefinsof the formula cyclo-[CX═CY(CZW)n-], wherein X, Y, Z, and W,independently, are H or F, and n is an integer from 2 to 5; and (iii)fluoroolefins selected from the group consisting of: hexafluoropropene(CF₃CF═CF₂); 1,2,3,3,3-pentafluoro-1-propene (CHF═CFCF₃),1,1,3,3,3-pentafluoro-1-propene (CF₂═CHCF₃),1,1,2,3,3-pentafluoro-1-propene (CF₂═CFCHF₂),1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF₂),2,3,3,3-tetrafluoro-1-propene (CH₂═CFCF₃), 1,3,3,3-tetrafluoro-1-propene(CHF═CHCF₃), 1,1,2,3-tetrafluoro-1-propene (CF₂═CFCH₂F),1,1,3,3-tetrafluoro-1-propene (CF₂═CHCHF₂),1,2,3,3-tetrafluoro-1-propene (CHF═CFCHF₂), 3,3,3-trifluoro-1-propene(CH₂═CHCF₃), 2,3,3-trifluoro-1-propene (CHF₂CF═CH₂);1,1,2-trifluoro-1-propene (CH₃CF═CF₂); 1,2,3-trifluoro-1-propene(CH₂FCF═CF₂); 1,1,3-trifluoro-1-propene (CH₂FCH═CF₂);1,3,3-trifluoro-1-propene (CHF₂CH═CHF);1,1,1,2,3,4,4,4-octafluoro-2-butene (CF₃CF═CFCF₃);1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₃CF₂CF═CF₂);1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF═CHCF₃);1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF₂CF₃);1,1,1,2,3,4,4-heptafluoro-2-butene (CHF₂CF═CFCF₃);1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene ((CF₃)₂C═CHF);1,1,3,3,4,4,4-heptafluoro-1-butene (CF₂═CHCF₂CF₃);1,1,2,3,4,4,4-heptafluoro-1-butene (CF₂═CFCHFCF₃);1,1,2,3,3,4,4-heptafluoro-1-butene (CF₂═CFCF₂CHF₂);2,3,3,4,4,4-hexafluoro-1-butene (CF₃CF₂CF═CH₂);1,3,3,4,4,4-hexafluoro-1-butene (CHF═CHCF₂CF₃);1,2,3,4,4,4-hexafluoro-1-butene (CHF═CFCHFCF₃);1,2,3,3,4,4-hexafluoro-1-butene (CHF═CFCF₂CHF₂);1,1,2,3,4,4-hexafluoro-2-butene (CHF₂CF═CFCHF₂);1,1,1,2,3,4-hexafluoro-2-butene (CH₂FCF═CFCF₃);1,1,1,2,4,4-hexafluoro-2-butene (CHF₂CH═CFCF₃);1,1,1,3,4,4-hexafluoro-2-butene (CF₃CH═CFCHF₂);1,1,2,3,3,4-hexafluoro-1-butene (CF₂═CFCF₂CH₂F);1,1,2,3,4,4-hexafluoro-1-butene (CF₂═CFCHFCHF₂);3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH₂═C(CF₃)₂);1,1,1,2,4-pentafluoro-2-butene (CH₂FCH═CFCF₃);1,1,1,3,4-pentafluoro-2-butene (CF₃CH═CFCH₂F);3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂);1,1,1,4,4-pentafluoro-2-butene (CHF₂CH═CHCF₃);1,1,1,2,3-pentafluoro-2-butene (CH₃CF═CFCF₃);2,3,3,4,4-pentafluoro-1-butene (CH₂═CFCF₂CHF₂);1,1,2,4,4-pentafluoro-2-butene (CHF₂CF═CHCHF₂);1,1,2,3,3-pentafluoro-1-butene (CH₃CF₂CF═CF₂);1,1,2,3,4-pentafluoro-2-butene (CH₂FCF═CFCHF₂);1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF₂═C(CF₃)(CH₃));2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH₂═C(CHF₂)(CF₃));2,3,4,4,4-pentafluoro-1-butene (CH₂═CFCHFCF₃);1,2,4,4,4-pentafluoro-1-butene (CHF═CFCH₂CF₃);1,3,4,4,4-pentafluoro-1-butene (CHF═CHCHFCF₃);1,3,3,4,4-pentafluoro-1-butene (CHF═CHCF₂CHF₂);1,2,3,4,4-pentafluoro-1-butene (CHF═CFCHFCHF₂);3,3,4,4-tetrafluoro-1-butene (CH₂═CHCF₂CHF₂);1,1-difluoro-2-(difluoromethyl)-1-propene (CF₂═C(CHF₂)(CH₃));1,3,3,3-tetrafluoro-2-methyl-1-propene (CHF═C(CF₃)(CH₃));3,3-difluoro-2-(difluoromethyl)-1-propene (CH₂═C(CHF₂)₂);1,1,1,2-tetrafluoro-2-butene (CF₃CF═CHCH₃); 1,1,1,3-tetrafluoro-2-butene(CH₃CF═CHCF₃); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene(CF₃CF═CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene(CF₂═CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene((CF₃)₂C═CHCF₃); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene(CF₃CF═CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene(CF₃CH═CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene(CHF═CFCF₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene(CF₂═CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene(CF₂═CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene(CHF₂CF═CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene(CF₃CF═CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene(CF₃CF═CFCHFCF₃); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene(CHF═CFCF(CF₃)₂); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene(CF₂═CFCH(CF₃)₂); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene(CF₃CH═C(CF₃)₂); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene(CF₂═CHCF(CF₃)₂); 2,3,3,4,4,5,5,5-octafluoro-1-pentene(CH₂═CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene(CHF═CFCF₂CF₂CHF₂); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene(CH₂═C(CF₃)CF₂CF₃); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene(CF₂═CHCH(CF₃)₂); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene(CHF═CHCF(CF₃)₂); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene(CF₂═C(CF₃)CH₂CF₃); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene((CF₃)₂CFCH═CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF₃CF₂CF₂CH═CH₂);2,3,3,4,4,5,5-heptafluoro-1-pentene (CH₂═CFCF₂CF₂CHF₂);1,1,3,3,5,5,5-heptafluoro-1-butene (CF₂═CHCF₂CH₂CF₃);1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF₃CF═C(CF₃)(CH₃));2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH₂═CFCH(CF₃)₂);1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CHF═CHCH(CF₃)₂);1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH₂FCH═C(CF₃)₂);1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH₃CF═C(CF₃)₂);1,1,1-trifluoro-2-(trifluoromethyl)-2-butene ((CF₃)₂C═CHCH₃);3,4,4,5,5,5-hexafluoro-2-pentene (CF₃CF₂CF═CHCH₃);1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF₃C(CH₃)═CHCF₃);3,3,4,5,5,5-hexafluoro-1-pentene (CH₂═CHCF₂CHFCF₃);4,4,4-trifluoro-2-(trifluoromethyl)-1-butene (CH₂═C(CF₃)CH₂CF₃);1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF₃(CF₂)₃CF═CF₂);1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF₃CF₂CF═CFCF₂CF₃);1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene((CF₃)₂C═C(CF₃)₂);1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene((CF₃)₂CFCF═CFCF₃);1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene((CF₃)₂C═CHC₂F₅);1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene((CF₃)₂CFCF═CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene(CF₃CF₂CF₂CF₂CH═CH₂); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene(CH₂═CHC(CF₃)₃);1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene((CF₃)₂C═C(CH₃)(CF₃));2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene(CH₂═CFCF₂CH(CF₃)₂); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene(CF₃CF═C(CH₃)CF₂CF₃);1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene (CF₃CH═CHCH(CF₃)₂);3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF₃CF₂CF₂CF═CHCH₃);3,3,4,4,5,5,6,6-octafluoro1-hexene (CH₂═CHCF₂CF₂CF₂CHF₂);1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene ((CF₃)₂C═CHCF₂CH₃);4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene (CH₂═C(CF₃)CH₂C₂F₅);3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF₃CF₂CF₂C(CH₃)═CH₂);4,4,5,5,6,6,6-heptafluoro-2-hexene (CF₃CF₂CF₂CH═CHCH₃);4,4,5,5,6,6,6-heptafluoro-1-hexene (CH₂═CHCH₂CF₂C₂F₅);1,1,1,2,2,3,4-heptafluoro-3-hexene (CF₃CF₂CF═CFC₂H₅);4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene (CH₂═CHCH₂CF(CF₃)₂);1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF₃CF═CHCH(CF₃)(CH₃));1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene ((CF₃)₂C═CFC₂H₅);1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene(CF₃CF═CFCF₂CF₂C₂F₅);1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene(CF₃CF₂CF═CFCF₂C₂F₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene(CF₃CH═CFCF₂CF₂C₂F₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene(CF₃CF═CHCF₂CF₂C₂F₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene(CF₃CF₂CH═CFCF₂C₂F₅); and1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF₃CF₂CF═CHCF₂C₂F₅).2. The process of claim 1, wherein said extracting comprises aliquid-liquid extraction.
 3. The process of claim 1 comprising: a.feeding a composition comprising HF and fluoroolefin and a compositioncomprising extractant to an extractor; and b. removing from saidextractor an extractant-rich phase comprising extractant andfluoroolefin.
 4. The process of claim 3 further comprising: a. feedingthe extractant-rich phase comprising extractant and fluoroolefin to anextractant recovery column; and b. recovering fluoroolefin productessentially free of extractant from the extractant recovery column. 5.The process of claim 1 comprising: a. feeding a composition comprisingHF and fluoroolefin and a composition comprising extractant to anextractor; and b. removing from said extractor an HF-rich phase.
 6. Theprocess of claim 5 further comprising: a. feeding said HF-rich phase toa raffinate stripping column; and b. recovering from said raffinatestripping column HF product essentially free of fluoroolefin andextractant.
 7. The process of claim 1 comprising: a. feeding acomposition comprising HF and fluoroolefin and a composition comprisingextractant to an extractor; b. removing from said extractor anextractant-rich phase comprising extractant and fluoroolefin; c.removing from said extractor an HF-rich phase; d. feeding saidextractant-rich phase comprising extractant and fluoroolefin to anextractant recovery column; e. recovering fluoroolefin productessentially free of extractant from the extractant recovery column; f.feeding said HF-rich phase to a raffinate stripping column; and g.recovering from said raffinate stripping column HF product essentiallyfree of fluoroolefin and extractant.
 8. The process of claim 3, 5, or 7,wherein said extractor operates at a pressure of from about 14.7 psia toabout 300 psia and a temperature from about −50° C. to about 150° C. 9.The process of claim 4 or 7, wherein said extractant recovery columnoperates at a pressure of about 14.7 psia to about 300 psia and a toptemperature of about −50° C. to about 100° C. and a bottom temperatureof about 50° C. to about 250° C.
 10. The process of claim 6 or 7,wherein said raffinate stripping column operates at a pressure of about14.7 psia to about 100 psia and a top temperature of about −50° C. toabout 90° C. and a bottom temperature from about 20° C. to about 100° C.11. The process of claim 1 wherein said extractant is selected from thegroup consisting of: ethane, ethylene, n-propane, propylene, n-butane,isobutane, cyclobutane, 1-butene, 2-butene (cis or trans), n-pentane,isopentane (2-methylbutane), neopentane (2,2-dimethylpropane),cyclopentane, 1-pentene, 2-pentene (cis or trans), cyclopentene,n-hexane, cyclohexane, 2-methylpentane, 3-methylpentane, 1-hexene,2-hexene (cis or trans), 3-hexene (cis or trans), neohexane(2,2-dimethylbutane), neohexene (3,3-dimethyl-1-butene),2,2-dimethylbutane, 2,3-dimethylbutane, 2,3-dimethyl-2-butene,2,3-dimethyl-1-butene, 3,3-dimethyl-1-butene, n-heptane, 1-heptene,2-heptene (cis or trans), 3-heptene (cis or trans), cycloheptene, octane(all isomers), nonane (all isomers), decane (all isomers), undecane (allisomers), dodecane (all isomers), benzene, toluene, tetrachloroethylene,trichloroethylene, 1,1-dichloroethylene, 1,2-dichloroethylene, carbontetrachloride (tetrachloromethane), chloroform (trichloromethane),methylene chloride (dichloromethane), 1,1,2,2-tetrachloroethane,1,1,1,2-tetrachloroethane, 1,1,2-trichloroethane, 1,1,1-trichloroethane,1,1,1,3,3,3-hexachloropropane, dichlorodifluoromethane (CFC-12),fluorotrichloromethane (CFC-11), fluoropentachloroethane (CFC-111),1,2-difluoro-1,1,2,2-tetrachloroethane (CFC-112),1,1-difluoro-1,2,2,2-tetrachloroethane (CFC-112a),1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113),1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a),1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114),1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a), andchloropentafluoroethane (CFC-115), dichlorofluoromethane (HCFC-21),1,1,2-trichloro-2,2-difluoroethane (HCFC-122),2,2-dichloro-1,1,1-trifluoroethane (HCFC-123),1,2-dichloro-1,1,1-trifluoroethane (HCFC-123a),2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124),1-chloro-1,1,2,2-tetrafluoroethane (HCFC-124a),1-chloro-1,2,2-trifluoroethane (HCFC-133),2-chloro-1,1,1-trifluoroethane (HCFC-133a), 1,1-dichloro-2-fluoroethane(HCFC-141a), 1,1-dichloro-1-fluoroethane (HCFC-141b),1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-1,1-difluoroethane(HCFC-142b), 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane(HFC-63-14mcee), 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, HFC-162-13mczy,1,2,3,3,3-pentafluoro-1-propene (HFC-1225ye),1,1,3,3,3-pentafluoro-1-propene (HFC-1225zc),1,3,3,3-tetrafluoro-1-propene (HFC-1234ze),2,3,3,3-tetrafluoro-1-propene (HFC-1234yf),3,3,3-trifluoro-1-propene(HFC-1243zf),1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429myz),1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429mzy),1,1,1,4,4,4-hexafluoro-2-butene (F11E),1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E),1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluoro-3-octene (F24E),1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluoro-4-octene (F33E),fluorobenzene, octafluoropropane (PFC-218), octafluorocyclobutane(PFC-C318), all isomers of C₄F₁₀ (PFC-31-10), hexafluoropropylene (HFP,PFC-1216), all isomers of C₅F₁₂ (PFC-41-12), all isomers of C₆F₁₄(PFC-51-14), PMVE (perfluoromethylvinylether), PEVE(perfluoroethylvinylether), and mixtures thereof.
 12. The process ofclaim 1, wherein the fluoroolefin comprises a fluoropropene.
 13. Theprocess of claim 1, wherein the fluoroolefin is Z-HFC-1225ye,E-HFC-1225ye, or any combination or mixture of both isomers in anyratio.
 14. The process of claim 1, wherein the fluoroolefin isHFC-1234yf.
 15. The process of claim 1, wherein the fluoroolefin isZ-HFC-1234ze, E-HFC-1234ze, or any combination or mixture of bothisomers in any ratio.
 16. The process of claim 1, wherein saidfluoroolefin is selected from the group consisting of:1,1,1,4,4,4-hexafluorobut-2-ene; 1,1,1,4,4,5,5,5-octafluoropent-2-ene;1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene;1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene;1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene;1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene;1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene;1,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)hex-2-ene;1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene;1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene;1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene;1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-ene;1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyphept-2-ene;1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hex-2-ene;1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene;1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-3-ene;1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)hept-3-ene;1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3-ene;1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene;1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3-ene;1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept-3-ene;1,1,1,4,4,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-2-ene;1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethyl)hept-2-ene;1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-ene;1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene;1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-3-ene;1,1,1,2,2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyl)hept-3-ene;1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene;1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-4-ene;1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-(trifluoromethyl)oct-4-ene;1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)hept-3-ene;1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifluoromethyl)oct-3-ene;1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)hept-3-ene;1,1,1,2,5,6,6,7,7,7-decafluoro-2,5-bis(trifluoromethyl)hept-3-ene;1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3-ene;1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-3-ene;1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)non-3-ene;1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5-bis(trifluoromethyl)oct-3-ene;1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-4-ene;1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-(trifluoromethyl)non-4-ene;1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6-bis(trifluoromethyl)oct-4-ene;1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-3-ene;1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct-3-ene;1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)hept-3-ene;1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluorodec-5-ene;1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-4-ene;1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-(trifluoromethyl)non-4-ene;1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,-bis(trifluoromethyl)oct-3-ene;1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct-4-ene;1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6-bis(trifluoromethyl)oct-4-ene;1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)hept-3-ene;1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-bis(trifluoromethyl)oct-4-ene;1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-bis(trifluoromethyl)oct-4-ene;1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)hept-3-ene; and1,1,1,6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl)hex-3-ene. 17.The process of claim 1, wherein said fluoroolefin is selected from thegroup consisting of: 1,2,3,3,4,4-hexafluorocyclobutene;3,3,4,4-tetrafluorocyclobutene; 3,3,4,4,5,5,-hexafluorocyclopentene;1,2,3,3,4,4,5,5-octafluorocyclopentene; and1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene.